Reaction products of aliphatic alco



stantial extent aflected Patented Aug. 15, 194 4 REACTION PRODUCTS OFTIC ALCO- ALIPHA HOLB AND TEBPENE-PHOSPHORUS SUL- PHIDE 1 Robert L. May,Chicago, 11L, assignor to Sinclair Refining Company,

tion of Maine New York, N. Y., a corpora- No mm. Application July 14,194:,

- Seth-1N 5 Claims- (cl. 260-125) This invention relates to a novelcomposition of matter and more particularly to a new class of compoundsresulting from the reaction of an alcohol with a condensation product ofturpentine and a phosphorus sulphide.

In my co-pending application Serial No. 494,688, filed July 14, 1943, Ihave described and claimed a new class of resin-like materials resultingfrom the condensation of certain phosphorus sulphides, includingphosphorus pentasuiphide, with a terpene such as turpentine. I have nowdiscovered that the condensation products of turpentine and Phosphoruspentasulphide, therein described, react with alcohols, more particularlyaliphatic alcohols, to form a new class of compounds of markedcommercial value particularly as addends in lubricating oils, as morefully described in my co-pending application Serial No. 494,690, filedmaterials in products.

The characteristics of the product of my present invention vary somewhatdepending upon the characteristics of the turpentine-Pass condensationproduct, and the nature and proportions of the alcohol used in itsproduction. Generally, these compounds are relatively acidic and arehighly soluble in mineral oils.

The invention will hereinafter be illustrated by specific examples of mynew products. Since the characteristics of the products are to a subbythe characteristics of the turpentine-Pass condensation product used inits preparation, description of the preparation of the condensationproducts used is included in these specific examples. Accordingly, thedethe synthesis of other valuable scrlption of the preparation of thevarious products will include two steps, 1. e., the preparation of theintermediate material and the preparation of the final product. However,it will be understood that' the compounds of my present invention may beprepared from a previoushr prepared turpentine-Pass condensationproduct.

In the preparation of the intermediate condensation products for use inthe preparation of the products of my present invention, the ratio ofturpentine to Pass used is with advantage within the range fromapproximately 1:1 to about 3 parts of turpentine to 1 part of Pass.Where ratios higher than about 3:1 are used, the product has been foundto contain considerable unreacted turpentine. Ratios of about 3:2 havegenerally been found to give particularly desirable results.

The reaction of turpentine with P235 is highly July 14, 1943, and asintermediate exothermic and proceeds spontaneously after being initiatedby slight heating. A desirable method of effecting the reaction is toheat the turpentine in a vessel to about 200 F. or slightly higher andthen, without further heating, slowly stirring in the phosphoruspentasulphide in the powdered form. The heat of the reaction is great,and, consequently, the addition should be madeslowly so as to avoid thepossibility of the reactions becoming uncontrollable. The product of mypresent invention is favorably affected by the use of a turpentine-Pisscondensation product in the preparation of which the temperature duringthe mixing is not permitted to exceed about 250 F., although highertemperatures are permissible.

After the addition is completed, it is usually necessary to apply heatexternally to complete the reaction. The temperature during this laststage is preferably maintained at about 300 F., though temperatures ofabout 200 to 400 F. may be employed. The second stage should becontinued until all of the Pass is dissolved. The material thus preparedis a viscous liquid at elevated temperatures which solidifies on coolingto room temperature.

In general, compounds of'the class of my present invention may beprepared by adding the alcohol gradually to the turpentine-Passcondensation product, advantageously at a temperature of about 250 withthe turpentin -P2Ss condensation product, very little heat is evolved.After the alcohol has been added, the mixture i's maintained at anelevated temperature, advantageously about F., for about 2 hours withstirring. The nature and proportions of the alcohol to be added may bevaried over a considerable range, depending upon the particularcharacteristics of the product desired. The proportion of alcohol usedis also dependent upon the ratio of turpentine to P280 used in thepreparation of the intermediate material. Particularly desirable resultshave been obtained using about 2 moles of PzSs, 5 moles turpentineand 3moles alcohol, assumilrg5 the molecular weight of the turpentine to be Icannot at present definitely identify this novel class of materials bychemical formula. However, in the preparation of the turpentine- Passcondensation product used in the preparation of these new materials, Ihave found it desirable that no unreacted Pass be present as in thetreatment 01' the turpentine-Pass condensation product with the alcohol,any unreacted F. In reacting the alcohol about 4 hours.

30 minutes.

the sulphide were added at first and,

.ceed 250 s Pass present has been found to react. with the alcohol toform esters of thiophosphoric acid.

The following. specific examples of various members and the procedure bywhich they have been successfully prepared are given as illustrative ofthe group: I

" Example I In a 3-liter, 3-necked flask .equippedwith a sulphide hadbeen added and the exothermic reactionhad stopped, as shown by adropping of the temperature, on and the mixture 300 F., and maintainedat that temperature for At the end of this Period all of the phosphoruspentasulphide was dissolved and the productwas a viscous amber coloredliquid. The heater was then turned 01! and the mixture allowed to coolto 250 F., and, whfle at this temperature, 780 grams (6 moles) of caprylalcohol (octanol-2) was added slowly. over a period of the heater wasagain turned hours.

The resultant product was found by analysis to have an acid number of71,- a saponiflcation number of 162.9 and to contain 8.07% phosphorusand 20.3% sulphur, each by weight, 5 v I Example v In a 5-liter flask,similar to that used in Example I, there was placed 2040 grams (15moles) of steam-distilled wood turpentine.

tine was then heated to about 200 F., by means of an electric heaterplaced under the flask. Thereafter, the heat was turnedofl' and 1332'grams (6 moles) of powdered phosphorus pentasulphide was. addedportionwise and stirred into period, the phosphorus pentasulphide-wasdissolved. The heater was then turned oft, the

was added: portions of pentasulphide so thatit did not ex stirredandheated slowly tov The heater was again turned on, and the te peratureheld at 200P220 F. for 2.

heated tof maintained at I and to contain 8.2% phosphorus and 20.8%sulphur by weight.

Example III .that the temperature did not rise above 250 F.

After all the sulphide had been added, the temperature of the mixturewas raised to 300 1". and that temperature for about 3 hours, at the endof which period all of the phos- 1 264 grains of Pentasol,"

of amyl alcohols, was added. The temperature The first half ot thephosphorus held at about 200 to 220 the addition of the alcohol.

contents of the flask permitted to cool to 250 F,

The product resulting from the above described procedure was found byanalysis to have an acid number 01564.9, a ,saponiflcation number of156.8 7

5 number oi 176.2 and phorus and 22.1% sulphur by weight.

phorus pentasulphidewas dissolved. The mixture was then permitted tocool to 250 F. and a commercial mixture was. then maintained at 220 F.for an additional hour.

The product was found by analysis to have an acid number of 74.6 andasaponiflcation number of 181.1 and to contain 9.23% phosphorus and21.57% sulphur by weight.

Example IV after, the mixture was cooled to 250 F. and 30s ber of 172.1and, to contain 8.20% phosphorus and 21.57% sulphur by weight.

Example V 680 grams (5 moles) of steam-distilled wood turpentine wasplaced in ail-liter flask, such as previously described, and heated to225 F. There was then added 444 powdered phosphorus pentasulphide, in 25to 30 gram portions, at such a rate as to hold the temperature below2501 F. No external heat was applied during this addition. When all; 01"the phosphorus pentasulphide was added, the mixture was heated to 300 F.and maintained at temperature for 3-hours, at the end of whichperiod thephosphorus pentasulphide had dissolved. Themixture was then 'cooled' toF., and 306 grams (3 moles) of 2-ethyl butanol-l was added over a periodor 30 minutes with continuousstirring. Th temperature was F. for 1 hourafter The product was found by analysisto have an acid to contain 8.96%phosrsom ze v1 340 grams (2.5 moles) of turpentine was heated to 200 F.and 222 grams (1 mole) oi powdered phosphorus entasulphide was addedslowly as previously described. After the phoswa heated to 200 1a, the

grams (2 moles) ofphorus pentasulphide was all dissolved, 279 grams (1.5moles) of Lorol, a commercial mixture of alcohols made from hydrogenatedfatty acid esters from palm oil and containing from to 14 carbon atomsper molecule, was added and the-mixture maintained for temperature of220 F.

The product was found by analysis to have an acid number of 61.2 and asaponiflcation number of 147.3 and to contain 7.18% phosphorus and19.80% sul hur by weight.

Example VII To a turpentine-Pass condensation product prepared as inExample VI, there was added 405 grams (1.5 moles) of octadecyl alcoholand the mixture maintained at 220 F. for 1 hour. product was found byanalysis to have an acid number of 57.2 and a saponiflcation number of131.6 and to I contain 6.52% phosphorus and 17.20% sulphur by weight..

Example VIII powdered phorphorus pentasulphide was then slowly added tothe heated turpentine under conditions described in Example I. After thephosphorus pentasulphide was dissolved, 1300 grams (10 moles) oi caprylalcohol (octano1-2) was added and the mixture stirred and heated as inExample I. The product was found by analysis to have an acid number of114.2 and a saponiflcation number of 146.9 and to contain 7.09%phosphorus and 17.4% sulphur, by weight.

Example IX 1 hour at a The.

ing from methyl to octadecyl alcohol, i. e., containing from 1 to 18carbon atoms per molecule, including secondary alcohols of 5 to 8 carbonatoms and branched chain primary alcohols containing 5 to 6 carbonatoms, have been used with advantage. Products having particularlydesirable characteristics, especially as constituents of lubricating oilcompositions, have been obtained by the use of capryl alcohol(octanol-2). Also, normal hexyl alcohol and lauryl alcohol have beenused with exceptional advantage in the preparation of products for suchpurposes. Generally, aliphatic alcohols having 5 or more car-v bon atomsper molecule are preferred.

The turpentine-P285 condensation product from which the members of mynew class of compounds are prepared is, in the absence of excessturpentine, normally a brittle, resinous solid. It is with advantageprepared from turpentine, either steam-distilled wood turpentine or gumspirits, consisting mainly of alpha pinene, a bi-cyclie terpene havingthe empirical formula CioHu. Pure alpha pinene and other more costlyterpenes will react similarly with P285 but, for reasons includingeconomic considerations, I prefer to use the more readily availableturpentines. The turpentine used in the specific examples herein was atechnical grade steam-distilled wood turpentine comprising about 90%alpha pinene.

Iclaim:

l. The product resulting from the reaction of an aliphatic alcohol witha condensation product of turpentinaand phosphorus pentasulphide.

2. The roduct resulting from the reaction of an aliphatic alcohol, ofnot less than 5 carbon atoms per molecule, with a condensation productof turpentine and phosphorus pentasulphide.

3. The product resulting from the reaction of capryl alcohol with acondensation product of turpentine and hosphorus pentasulphide.

4. The product resulting from the reaction of normal hexyl alcohol witha condensation product of turpentine and phosphorus pentasulphide.

5. The product resulting from the reaction of lauryl alcohol with acondensation product of turpentine and phosphorus pentasulphide.

ROBERT L. MAY.

CERTIFICATE OF C ORRECTION Patent No. 2,} 56,075

ROBERT L. MAY.

August .15, 119ml.

It is hereby certified that error appears in the printed specificationof the above numbered patent requiring correction as follows: P ge 5first column, line 59, for

"Example VII" read --Example VIII--; and that the said Letters Patent.should be read with this correction therein that the same may conform tothe (Seal) record of the case Signed and sealed this 51st day ofOctober,

i the Patent Office.

A. D. 19th,.

Leslie Frazer Acting Commissioner of Patents.

phorus pentasulphide was all dissolved, 279 grams (1.5 moles) of Lorol,a commercial mixture of alcohols made from hydrogenated fatty acidesters from palm oil and containing from to 14 carbon atoms permolecule, was added and the-mixture maintained for temperature of 220 F.

The product was found by analysis to have an acid number of 61.2 and asaponiflcation number of 147.3 and to contain 7.18% phosphorus and19.80% sul hur by weight.

Example VII To a turpentine-Pass condensation product prepared as inExample VI, there was added 405 grams (1.5 moles) of octadecyl alcoholand the mixture maintained at 220 F. for 1 hour. product was found byanalysis to have an acid number of 57.2 and a saponiflcation number of131.6 and to I contain 6.52% phosphorus and 17.20% sulphur by weight..

Example VIII powdered phorphorus pentasulphide was then slowly added tothe heated turpentine under conditions described in Example I. After thephosphorus pentasulphide was dissolved, 1300 grams (10 moles) oi caprylalcohol (octano1-2) was added and the mixture stirred and heated as inExample I. The product was found by analysis to have an acid number of114.2 and a saponiflcation number of 146.9 and to contain 7.09%phosphorus and 17.4% sulphur, by weight.

Example IX 1 hour at a The.

ing from methyl to octadecyl alcohol, i. e., containing from 1 to 18carbon atoms per molecule, including secondary alcohols of 5 to 8 carbonatoms and branched chain primary alcohols containing 5 to 6 carbonatoms, have been used with advantage. Products having particularlydesirable characteristics, especially as constituents of lubricating oilcompositions, have been obtained by the use of capryl alcohol(octanol-2). Also, normal hexyl alcohol and lauryl alcohol have beenused with exceptional advantage in the preparation of products for suchpurposes. Generally, aliphatic alcohols having 5 or more car-v bon atomsper molecule are preferred.

The turpentine-P285 condensation product from which the members of mynew class of compounds are prepared is, in the absence of excessturpentine, normally a brittle, resinous solid. It is with advantageprepared from turpentine, either steam-distilled wood turpentine or gumspirits, consisting mainly of alpha pinene, a bi-cyclie terpene havingthe empirical formula CioHu. Pure alpha pinene and other more costlyterpenes will react similarly with P285 but, for reasons includingeconomic considerations, I prefer to use the more readily availableturpentines. The turpentine used in the specific examples herein was atechnical grade steam-distilled wood turpentine comprising about 90%alpha pinene.

Iclaim:

l. The product resulting from the reaction of an aliphatic alcohol witha condensation product of turpentinaand phosphorus pentasulphide.

2. The roduct resulting from the reaction of an aliphatic alcohol, ofnot less than 5 carbon atoms per molecule, with a condensation productof turpentine and phosphorus pentasulphide.

3. The product resulting from the reaction of capryl alcohol with acondensation product of turpentine and hosphorus pentasulphide.

4. The product resulting from the reaction of normal hexyl alcohol witha condensation product of turpentine and phosphorus pentasulphide.

5. The product resulting from the reaction of lauryl alcohol with acondensation product of turpentine and phosphorus pentasulphide.

ROBERT L. MAY.

CERTIFICATE OF C ORRECTION Patent No. 2,} 56,075

ROBERT L. MAY.

August .15, 119ml.

It is hereby certified that error appears in the printed specificationof the above numbered patent requiring correction as follows: P ge 5first column, line 59, for

"Example VII" read --Example VIII--; and that the said Letters Patent.should be read with this correction therein that the same may conform tothe (Seal) record of the case Signed and sealed this 51st day ofOctober,

i the Patent Office.

A. D. 19th,.

Leslie Frazer Acting Commissioner of Patents.

